WO2013076765A1 - Module de conversion thermoélectrique - Google Patents

Module de conversion thermoélectrique Download PDF

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Publication number
WO2013076765A1
WO2013076765A1 PCT/JP2011/006512 JP2011006512W WO2013076765A1 WO 2013076765 A1 WO2013076765 A1 WO 2013076765A1 JP 2011006512 W JP2011006512 W JP 2011006512W WO 2013076765 A1 WO2013076765 A1 WO 2013076765A1
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WIPO (PCT)
Prior art keywords
alloy
thermoelectric conversion
conversion module
group
thermal stress
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PCT/JP2011/006512
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English (en)
Japanese (ja)
Inventor
孝洋 越智
尚吾 鈴木
昌晃 菊地
慧遠 耿
伊藤　哲
俊清 郭
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古河機械金属株式会社
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Application filed by 古河機械金属株式会社 filed Critical 古河機械金属株式会社
Priority to PCT/JP2011/006512 priority Critical patent/WO2013076765A1/fr
Priority to EP11876342.4A priority patent/EP2784834B1/fr
Priority to US14/342,115 priority patent/US9337409B2/en
Publication of WO2013076765A1 publication Critical patent/WO2013076765A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/82—Connection of interconnections
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/81—Structural details of the junction
    • H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered

Definitions

  • the present invention relates to a thermoelectric conversion module capable of directly converting heat energy into electricity or electricity into heat energy.
  • thermoelectric conversion member is a material that can directly convert thermal energy into electricity, or that can be heated and cooled by directly converting electrical energy into thermal energy, that is, by applying electricity.
  • thermoelectric conversion module If a large number of p / n thermoelectric conversion member pairs in which p-type thermoelectric conversion members and n-type thermoelectric conversion members are combined are electrically connected in series, one thermoelectric conversion module is formed. If a thermoelectric conversion module is used, waste heat, which has not been used so far, can be converted into electricity to effectively use energy.
  • thermoelectric conversion members used in the thermoelectric conversion module Bi 2 Te 3 system, PbTe system, AgSbTe 2 -GeTe system, SiGe system, (Ti, Zr, Hf) NiSn
  • thermoelectric conversion members Bi 2 Te 3 system, PbTe system, AgSbTe 2 -GeTe system, SiGe system, (Ti, Zr, Hf) NiSn
  • skutterudite and filled skutterudite typified by CoSb 3 , Zn 4 Sb 3 , FeSi 2 , NaCo 2 O 4, oxides Ca 3 Co 4 O 9 , and the like.
  • the temperature range that can be used for power generation is limited to the range of about 250 ° C. that the Bi 2 Te 3 system material can withstand from near room temperature.
  • thermoelectric conversion module that can be used in an intermediate temperature region of 300 ° C. to 600 ° C. is demanded in that various waste heat is effectively used.
  • thermoelectric conversion member having a filled skutterudite structure has attracted attention as a thermoelectric conversion member usable particularly in this temperature range.
  • the filled skutterudite compound is represented by the chemical formula RT 4 X 12 and has a cubic structure of the space group Im-3 (No. 204).
  • R is an alkaline earth metal, a lanthanoid or actinoid element
  • T is a transition metal such as Fe, Ru, Os, Co, Pd, and Pt
  • X is a nicotine element such as As, P, and Sb.
  • thermoelectric conversion member in which X is Sb has been actively studied.
  • the filled skutterudite-based thermoelectric conversion member exhibits high thermoelectric performance in such an intermediate temperature region.
  • thermoelectric conversion module When producing a thermoelectric conversion module using a thermoelectric conversion member, it is necessary to join each p-type and n-type thermoelectric conversion member and an electrode member at a high temperature part and a low temperature part.
  • the thermoelectric conversion module using the Bi 2 Te 3 series thermoelectric conversion member is used in a temperature range of 250 ° C. or lower.
  • thermoelectric conversion module that can be used in the middle temperature range of 300 ° C. to 600 ° C.
  • the selection of the material of the electrode member that connects the p-type thermoelectric conversion member and the n-type thermoelectric conversion member, and the joining method are required. This is an important issue.
  • thermoelectric conversion member It is essential that the electrode member and the thermoelectric conversion member have good bondability and that the performance deterioration of the thermoelectric conversion member due to the electrode member does not occur. In order to achieve this, it is essential to have consistency in the thermal expansion coefficient between the thermoelectric conversion member, the electrode member, and the material used for bonding in the operating temperature range up to 600 ° C., and the stability of the bonding layer at the bonding interface. It is.
  • thermoelectric performance deteriorates and the electrode member performance deteriorates.
  • thermoelectric conversion module can be manufactured using a filled skutterudite-based thermoelectric conversion member, an element with higher conversion efficiency in a higher temperature range than a thermoelectric conversion module using conventional Bi 2 Te 3 Can be used.
  • solder cannot be used at the junction between the thermoelectric conversion member and the electrode member in the high temperature portion.
  • thermoelectric conversion module has reached the end of its life without the performance of the original thermoelectric conversion member, and there has been a problem in terms of durability.
  • thermoelectric conversion module in which a titanium or titanium alloy alloy layer is provided between a thermoelectric conversion member and an electrode member in a high-temperature part related to a thermoelectric conversion member having a skutterudite structure.
  • thermoelectric conversion module having an n-type thermoelectric element and a p-type thermoelectric element
  • at least one of the n-type thermoelectric element and the p-type thermoelectric element has a thickness of 10 ⁇ m or more.
  • a titanium layer or a titanium alloy layer is formed.
  • a compound having a skutterudite type crystal structure is used as a material of an n-type element, and examples thereof include the following.
  • M1-AM′AXB represents any one of Co, Rh, and Ir
  • M ′ is a dopant for making n-type
  • Pd, Pt represents any one of PdPt
  • X represents any of As, P, and Sb, and satisfies the condition of 0 ⁇ A ⁇ 0.2 and 2.9 ⁇ B ⁇ 4.2 Things are suitable.
  • a compound having a simple composition ratio can be obtained.
  • a Co—Sb-based compound such as Co 0.9 (PdPt) 0.1 Sb 3 can be given.
  • Co 0.9 (PdPt) 0.1 Sb 3 instead of the Co 0.9 (PdPt) 0.1 Sb 3 , may be CoSb3 having the same structure as this.
  • M represents any one of Co, Rh, and Ir
  • X represents any one of As, P, and Sb
  • X ′ represents any of Te, Ni, and Pd, and those satisfying the condition of 0 ⁇ A ⁇ 0.1 are suitable.
  • M represents Co, Rh, or Ir
  • M ′ represents n-type.
  • X represents any one of As, P, and Sb
  • thermoelectric conversion module in the thermoelectric conversion module using the n-type and p-type thermoelectric elements having excellent characteristics up to a high temperature range around 500 ° C., diffusion of elements at the junction is prevented.
  • thermoelectric conversion module using the n-type and p-type thermoelectric elements having excellent characteristics up to a high temperature range around 500 ° C., diffusion of elements at the junction is prevented.
  • the thermal stress is generated due to the difference between the thermal expansion coefficient of the thermoelectric conversion member and the thermal expansion coefficient of the electrode member as the temperature rises, particularly at a temperature of 400 ° C. or higher. It is done.
  • the present invention has been made in view of the above-described problems, and can maintain good bonding between the thermoelectric conversion member and the electrode member even when the temperature changes significantly due to operation or the like, and the thermoelectric conversion member.
  • the thermoelectric conversion module which can prevent the spreading
  • thermoelectric conversion module of the present invention is a thermoelectric conversion module having a thermoelectric conversion member and an electrode member, wherein the thermoelectric conversion member and the electrode member are joined by a joining member, and the joining member is joined to the electrode member.
  • a thermal stress relaxation layer that relaxes thermal stress and a diffusion prevention layer that is bonded to the thermoelectric conversion member and prevents diffusion of constituent components, and the Young's modulus at 25 ° C. of the thermal stress relaxation layer is a thermoelectric conversion member And smaller than the electrode member.
  • thermoelectric conversion module of the present invention the bonding member that bonds the thermoelectric conversion member and the electrode member is bonded to the thermoelectric conversion member and the thermal stress relaxation layer that is bonded to the electrode member and relieves thermal stress. And a diffusion preventing layer for preventing the diffusion of the constituent components. Therefore, the thermal stress of the electrode member due to the operating temperature or the like is relaxed by the thermal stress relaxation layer, and the diffusion of the constituent components of the thermoelectric conversion member due to the operating temperature or the like is prevented by the diffusion preventing layer.
  • a member having a small Young's modulus is easily deformed, and stress is relieved by deformation at the joined portion of the joined different members.
  • the joining member having a small Young's modulus is deformed before the thermoelectric conversion member and the electrode member, so that the thermal stress can be relieved and the thermoelectric conversion member and the electrode member can be prevented from being broken.
  • thermoelectric conversion member has a Young's modulus at 25 ° C. of 140 MPa
  • the thermal stress relaxation layer preferably has a Young's modulus at 25 ° C. of 130 MPa or less.
  • the electrode member is made of at least one alloy selected from the group consisting of an Fe alloy, Ni alloy, Co alloy, Cu alloy, Ti alloy, and Al alloy, and reduces thermal stress.
  • the layer is made of at least one alloy selected from the group consisting of a Cu alloy, an Ag alloy, an Au alloy, an Al alloy, and an Mg alloy
  • the diffusion prevention layer is made of Fe-M1 (M1 is Cr, Mo, W, At least one element selected from the group consisting of V, Nb, Ta, Mn, Ti, Zr, Hf, C, Si, and Ge) alloy, Co-M1 alloy, Ni-M1 alloy, Ti-M2 (M2 is At least one element selected from the group consisting of Al, Ga, In, Cu, Ag, Au, Sn, Zn, Mg) alloy, Zr—M2 alloy, Hf—M2 alloy, VM2 alloy, Nb—M2 Together , Ta-M2 alloy, Cr-M2 alloy, Mo-M2 alloy, and, W-
  • the stress relaxation layer is made of Cu-M3 (M3 is Ag, Au, Cu, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, P, Bi, At least one element selected from the group consisting of Li, Mg, Cr), at least one selected from the group consisting of an alloy, an Ag-M3 alloy, an Au-M3 alloy, an Al-M3 alloy, and an Mg-M3 alloy It may be made of an alloy of
  • the joining member has a stress relaxation layer and a diffusion prevention layer joined together by a joining auxiliary layer
  • the stress relaxation layer is M4 (M4 is Cu, Ag, Au, Al , Mg, at least one element selected from the group consisting of Mg, M3 (M3 is Ag, Au, Cu, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, P, Bi, Li) And at least one element selected from the group consisting of Mg, Cr), and the auxiliary bonding layer is selected from the group consisting of an Fe alloy, Ni alloy, Co alloy, Cu alloy, Ti alloy, and Al alloy. It may be made of at least one kind of alloy.
  • the diffusion prevention layer contains M5 (M5 is at least one element selected from the group consisting of Fe, Co, Ni) in a range of 50 wt% to less than 100 wt%.
  • M1 is at least one element selected from the group consisting of Cr, Mo, W, V, Nb, Ta, Mn, Ti, Zr, Hf, C, Si, and Ge) exceeds 0% by weight and exceeds 50% by weight It may be made of M5-M1 alloy including:
  • the diffusion prevention layer is at least one selected from the group consisting of M6 (M6 is Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn).
  • M6 is Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn.
  • M2 is at least one element selected from the group consisting of Al, Ga, In, Cu, Ag, Au, Sn, Zn, and Mg). It may be made of an M6-M2 alloy containing more than 50% by weight and less than 50% by weight.
  • the difference in thermal expansion coefficient between the diffusion preventing layer and the thermoelectric conversion member at 20 ° C. to 600 ° C. may be 20% or less of the thermal expansion coefficient of the thermoelectric conversion member.
  • the thermal expansion coefficient of the diffusion preventing layer at 20 ° C. to 600 ° C. may be 8 ⁇ 10 ⁇ 6 (/ K) or more and 15 ⁇ 10 ⁇ 6 (/ K) or less. .
  • thermoelectric conversion member may be made of an Sb system having a skutterudite structure.
  • thermoelectric conversion member may have a filled skutterudite structure.
  • the general formula R r T t-m M m X x-n N n (0 ⁇ r ⁇ 1,3 ⁇ t-m ⁇ 5,0 ⁇ m ⁇ 0.5,10 ⁇ x ⁇ 15,0 ⁇ n ⁇ 2) having a filled skutterudite structure, wherein R is at least three selected from the group consisting of rare earth elements, alkali metal elements, alkaline earth metal elements, Group 4 elements and Group 13 elements T is at least one selected from Fe and Co, and M is at least selected from the group consisting of Ru, Os, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.
  • R-TM is characterized in that X is at least one selected from the group consisting of P, As, Sb and Bi, and N is at least one selected from Se and Te.
  • An -XN thermoelectric conversion member is desirable.
  • the difference in the thermal expansion coefficient between the thermoelectric conversion member and the joining member in the present invention means the absolute value of the difference between the thermal expansion coefficient of the thermoelectric conversion member and the thermal expansion coefficient of the joining member.
  • thermoelectric conversion module of the present invention the thermal stress of the electrode member due to the operating temperature and the like can be relaxed by the thermal stress relaxation layer, so that the electrode member can be favorably prevented from peeling due to the thermal stress of the operating temperature.
  • the diffusion of the components of the thermoelectric conversion member due to the operating temperature and the like can be prevented by the diffusion preventing layer, so that the durability and stability of the thermoelectric conversion module can be improved.
  • thermoelectric conversion module of embodiment of this invention It is a typical front view which shows the structure of the thermoelectric conversion module of embodiment of this invention. It is a typical front view which shows the structure of the thermoelectric conversion module of one modification. It is a typical front view which shows the structure of the thermoelectric conversion module of another modification.
  • FIG. 1 is a schematic diagram showing an example of a thermoelectric conversion module according to the present embodiment.
  • the thermoelectric conversion module 100 according to the present embodiment includes p-type and n-type thermoelectric conversion members 111 and 112 and electrode members 121 to 123.
  • thermoelectric conversion members 111 and 112 and the electrode members 121 to 123 are joined by the joining members 131 to 134, and the joining members 131 to 134 are joined to the electrode members 121 to 123.
  • the Young's modulus of the thermal stress relaxation layers 141 to 144 is smaller than that of the thermoelectric conversion members 111 and 112 and the electrode members 121 to 123. Since the thermoelectric conversion members 111 and 112 have a Young's modulus at 25 ° C. of 140 MPa, the thermal stress relaxation layers 141 to 144 preferably have a Young's modulus at 25 ° C. of 130 MPa or less.
  • the Fe alloy-based, Ni-alloy-based, Co-alloy-based, Cu-alloy-based, Ti-alloy-based, and Al-alloy-based electrode members have Young's modulus at 25 ° C. of about 200 MPa, 200 MPa, 200 MPa, 130 MPa, 120 MPa, and 70 MPa, respectively.
  • the thermal stress relaxation layers 141 to 144 corresponding to the material of these electrode members satisfy the condition that the Young's modulus at 25 ° C. is 130 MPa or less and employ a member smaller than the Young of the electrode member.
  • Thermoelectric conversion members 111 and 112 have the general formula R r T t-m M m X x-n N n (0 ⁇ r ⁇ 1,3 ⁇ t-m ⁇ 5,0 ⁇ m ⁇ 0.5,10 ⁇ x It consists of a compound having a filled skutterudite structure represented by ⁇ 15, 0 ⁇ n ⁇ 2).
  • R is composed of three or more elements selected from the group consisting of rare earth elements, alkali metal elements, alkaline earth metal elements, Group 4 elements and Group 13 elements, and T is at least selected from Fe and Co.
  • M is at least one selected from the group consisting of Ru, Os, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au, and X is made of P, As, Sb, and Bi. At least one selected from the group, and N is at least one selected from Se and Te.
  • thermoelectric conversion member 111 is an Sb-based compound having a filled skutterudite structure of (La, Ba, Ga, Ti) 0.7 to 1.0 (Fe, Co) 4 Sb 12 , and n-type.
  • the thermoelectric conversion member 112 is preferably an Sb-based compound having a filled skutterudite structure of (Yb, Ca, Al, Ga, In) 0.5 to 0.8 (Fe, Co) 4 Sb 12 .
  • the electrode members 121 to 123 are made of at least one alloy selected from the group consisting of an Fe alloy, Ni alloy, Co alloy, Cu alloy, Ti alloy, and Al alloy. In this embodiment, SUS430 or Cu is used. And a Cu alloy.
  • the thermal stress relaxation layers 141 to 144 are made of at least one alloy selected from the group consisting of a Cu alloy, an Ag alloy, an Au alloy, an Al alloy, and an Mg alloy. In this embodiment, the thermal stress relaxation layers 141 to 144 are made of an Ag alloy. Has been.
  • the thermal stress relaxation layers 141 to 144 may be formed of one kind of alloy layer as described above, but may be formed of two or more kinds of alloy layers.
  • the diffusion prevention layers 151 to 154 are Fe-M1 (M1 is at least one selected from the group consisting of Cr, Mo, W, V, Nb, Ta, Mn, Ti, Zr, Hf, C, Si, Ge) Element) alloy, Co-M1 alloy, Ni-M1 alloy, Ti-M2 (M2 is at least one element selected from the group consisting of Al, Ga, In, Cu, Ag, Au, Sn, Zn, Mg) ) Selected from the group consisting of alloys, Zr-M2 alloys, Hf-M2 alloys, V-M2 alloys, Nb-M2 alloys, Ta-M2 alloys, Cr-M2 alloys, Mo-M2 alloys, and W-M2 alloys Made of at least one kind of alloy.
  • the diffusion prevention layers 151 to 154 include 50% by weight or more and less than 100% by weight of M1 (M5 is at least one element selected from the group consisting of Fe, Co, Ni) and 0 M1. Made of M5-M1 alloy containing more than 50% by weight.
  • the diffusion prevention layers 151 and 152 bonded to the p-type thermoelectric conversion member 111 are Fe70 to 80 (wt%)-Cr 15 to 20 (wt%)-Si 0 to 10 (wt%) alloy. It is formed with.
  • the diffusion prevention layers 153 and 154 bonded to the n-type thermoelectric conversion member 111 are Fe60 to 70 (wt%)-Cr30 to 40 (wt%), Fe80 to 90 (wt%)-V10 to 20 (wt%). ), And Fe 70-80 (wt%)-Cr 10-15 (wt%)-V 5-15 (wt%).
  • the diffusion prevention layers 151 to 154 may be formed of one kind of alloy layer as described above, but may be formed of two or more kinds of alloy layers.
  • the thermal stress relaxation layers 141 to 144 are made of Cu-M3 (M3 is Ag, Au, Cu, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, P, Bi, Li, Mg, Cr). And at least one element selected from the group consisting of an Ag-M3 alloy, an Au-M3 alloy, an Al-M3 alloy, and an Mg-M3 alloy.
  • M3 is Ag, Au, Cu, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, P, Bi, Li, Mg, Cr.
  • the thermal stress relaxation layers 141 to 144 are made of Ag50 to 60 (wt%)-(Cu, Zn) 40 to 50 (wt%), Ag50 to 60 (wt%)-(Cu, Zn, Sn). ) It is made of 40-50 (wt%) alloy.
  • the difference in thermal expansion coefficient between the diffusion prevention layers 151 to 154 and the thermoelectric conversion members 111 and 112 at 20 ° C. to 600 ° C. is the thermal expansion of the thermoelectric conversion members 111 and 112. It is 20% or less of the coefficient. Further, the thermal expansion coefficient at 20 ° C. to 600 ° C. of the diffusion preventing layers 151 to 154 is 8 ⁇ 10 ⁇ 6 (/ K) or more and 15 ⁇ 10 ⁇ 6 (/ K) or less.
  • thermoelectric conversion module 100 of the present embodiment the joining members 131 to 134 that join the thermoelectric conversion members 111 and 112 and the electrode members 121 to 123 are joined to the electrode members 121 to 123.
  • the thermal stress of the electrode members 121 to 123 due to the operating temperature can be relaxed by the thermal stress relaxation layers 141 to 144, the peeling of the electrode members 121 to 123 due to the thermal stress of the operating temperature can be prevented well. Can do.
  • thermoelectric conversion module 100 the diffusion of the components of the thermoelectric conversion members 111 and 112 due to the operating temperature can be prevented by the diffusion preventing layers 151 to 154, so that the durability and stability of the thermoelectric conversion module 100 can be improved.
  • the Young's modulus of the thermal stress relaxation layers 141 to 144 is smaller than that of the thermoelectric conversion members 111 and 112 and the electrode members 121 to 123, and the Young's modulus at 25 ° C. is 130 MPa or less.
  • thermoelectric conversion module 100 Even if the temperature of the thermoelectric conversion module 100 becomes high due to the operation of the thermoelectric conversion module 100, the thermal stress of the thermoelectric conversion members 111 and 112 and the electrode members 121 to 123 can be well relaxed by the thermal stress relaxation layers 141 to 144. Therefore, it is possible to maintain good bonding between the thermal stress relaxation layers 141 to 144 and the electrode members 121 to 123.
  • thermoelectric conversion module 100 of the present embodiment the difference in thermal expansion coefficient between the diffusion prevention layers 151 to 154 and the thermoelectric conversion members 111 and 112 at 20 ° C. to 600 ° C. is the thermal expansion of the thermoelectric conversion members 111 and 112. It is 20% or less of the coefficient.
  • thermoelectric conversion module 100 Even when the temperature of the thermoelectric conversion module 100 is increased, the bonding between the diffusion prevention layers 151 to 154 and the thermoelectric conversion members 111 and 112 is maintained well.
  • thermoelectric conversion members 111 and 112 having a filled skutterudite structure usually have a thermal expansion coefficient of 20 ⁇ 10 ⁇ 6 at 20 ° C. to 600 ° C.
  • the range is (/ K) or more and 15 ⁇ 10 ⁇ 6 (/ K) or less.
  • the thermal expansion coefficient at 20 ° C. to 600 ° C. of the diffusion preventing layers 151 to 154 is 8 ⁇ 10 ⁇ 6 (/ K) or more and 15 ⁇ 10 ⁇ 6 (/ K) or less. For this reason, even when the temperature of the thermoelectric conversion module 100 is increased, the bonding between the thermoelectric conversion members 111 and 112 and the diffusion prevention layers 151 to 154 is favorably maintained.
  • the present invention is not limited to the present embodiment, and various modifications are allowed without departing from the scope of the present invention.
  • the thermal stress relaxation layers 141 to 144 and the diffusion prevention layers 151 to 154 of the bonding members 131 to 134 are directly bonded.
  • thermoelectric conversion module 200 illustrated in FIG. 2, the thermal stress relaxation layers 143 and 144 and the diffusion prevention layers 153 and 154 of the bonding members 133 and 134 bonded to the n-type thermoelectric conversion member 112 are bonded.
  • the auxiliary layers 213 and 214 may be joined.
  • the bonding auxiliary layers 213 and 214 have an effect that the thermal stress relaxation layers 143 and 144 and the diffusion preventing layers 153 and 154 are easily bonded. Since the material is the same as that of the electrode member, element diffusion between the thermal stress relaxation layers 143 and 144 and the diffusion prevention layers 153 and 154 can be prevented.
  • the thermal stress relaxation layers 141 to 144 are made of M4 (M4 is at least one element selected from the group consisting of Cu, Ag, Au, Al, Mg) —M3 alloy, for example, Ag56 (wt%) — A Cu22 (wt%)-Zn17 (wt%)-Sn5 (wt%) alloy is used.
  • the auxiliary bonding layers 213 and 214 are made of at least one alloy selected from the group consisting of an Fe alloy, Ni alloy, Co alloy, Cu alloy, Ti alloy, and Al alloy, and are formed of, for example, SUS430. .
  • the diffusion prevention layers 153 and 154 joined to the n-type thermoelectric conversion member 112 are Fe-M1 alloy, Co-M1 alloy, Ni-M1 alloy, Ti-M2 alloy, Zr-M2 alloy, Hf-M2 It is made of at least one alloy selected from the group consisting of alloys, V-M2 alloys, Nb-M2 alloys, Ta-M2 alloys, Cr-M2 alloys, Mo-M2 alloys, and W-M2 alloys.
  • M6 is at least one element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn
  • M6-M2 alloy containing less than and less than 0% by weight and less than 50% by weight of M2, and is formed of a Ti80Al20 (% by weight) alloy.
  • thermoelectric conversion module 200 the thermal stress relaxation layers 143 and 144 and the diffusion prevention layers 153 and 154 of the bonding members 133 and 134 bonded to the n-type thermoelectric conversion member 112 are bonded auxiliary layers 213 and 214. It is joined.
  • the auxiliary bonding layers 213 and 214 are made of at least one alloy selected from the group consisting of Fe alloy, Ni alloy, Co alloy, Cu alloy, Ti alloy, and Al alloy, which is the same material as the electrode member, and the thermal stress relaxation layer 143.
  • 144 and diffusion preventing layers 153 and 154 can be easily joined together, and element diffusion between thermal stress relaxation layers 143 and 144 and diffusion preventing layers 153 and 154 can be prevented.
  • joining auxiliary layers 213 and 214 and the electrode members 121 to 123 are formed of the same SUS430, a decrease in productivity due to the addition of the joining auxiliary layers 213 and 214 can be minimized.
  • thermoelectric conversion module 300 illustrated in FIG. 3, the thermal stress relaxation layers 141 to 144 and the diffusion prevention layers of the joining members 131 to 134 joined to the p-type and n-type thermoelectric conversion members 111 and 112. 151 to 154 may be joined by joining auxiliary layers 211 to 214.
  • the thermal stress relaxation layer is made of an M4-M3 alloy, for example, Cu 70 to 90 (wt%)-P 5 to 10 (wt%)-Ag 5 to 20 (wt%), and / or Cu 60 to 85 (wt%).
  • -P5-10 (wt%)-Ag5-15 (wt%)-Sn5-20 (wt%) alloy for example, Cu 70 to 90 (wt%)-P 5 to 10 (wt%)-Ag 5 to 20 (wt%), and / or Cu 60 to 85 (wt%).
  • the joining auxiliary layers 211 to 214 are made of at least one alloy selected from the group consisting of Fe alloy, Ni alloy, Co alloy, Cu alloy, Ti alloy, and Al alloy, which is the same material as the electrode member.
  • the thermal stress relaxation layers 141 to 144 and the diffusion prevention layers 151 to 154 have an effect of being easily joined, and element diffusion between the thermal stress relaxation layers 141 to 144 and the diffusion prevention layers 151 to 154 can be prevented. it can.
  • the electrode members 121 to 123 are also made of an M4-M3 alloy containing 50% by weight or more and less than 100% by weight of M4 and more than 0% by weight and 50% by weight or less of M3.
  • M4-M3 alloy containing 50% by weight or more and less than 100% by weight of M4 and more than 0% by weight and 50% by weight or less of M3.
  • it is made of a Cu50-60 (wt%)-Cr40-50 (wt%) alloy.
  • thermoelectric conversion module 300 since the thermal stress relaxation layers 141 to 144 and the diffusion prevention layers 151 to 154 of the bonding members 131 to 134 are bonded by the bonding auxiliary layers 211 to 214, the high temperature thermal stress due to the operation is increased. Therefore, it is possible to satisfactorily prevent the thermal stress relaxation layers 141 to 144 and the diffusion prevention layers 151 to 154 from peeling off.
  • auxiliary joining layers 211 to 214 and the electrode members 121 to 123 are made of the same Cu50-60 (wt%)-Cr40-50 alloy, productivity by adding the auxiliary joining layers 211-214 is increased. Can be minimized.
  • thermoelectric conversion module of the present invention will be specifically described by way of examples.
  • Table 1 shows the details of the members used in Examples 1 to 9.
  • thermoelectric conversion members 111 to 112, electrode members 121 to 123, and joining members 131 to 134 shown in Table 1 were prepared, and a temperature of 500 to 750 ° C., a pressure of 30 to 60 MPa, and inertness were obtained using a discharge plasma sintering method.
  • the auxiliary layers 211 to 214 were integrally joined, and then cut into 5 ⁇ 5 ⁇ 7.4 mm prismatic elements.
  • thermoelectric conversion module having an area of 50 ⁇ 50 mm 2 and a height of 8 mm was prepared by bonding to a p / n type prismatic element.
  • thermoelectric conversion module produced by the above method. Specifically, in a vacuum or an inert gas atmosphere, a block heater was used on the high temperature side, and the low temperature side was cooled to 50 ° C. or less by water cooling to conduct a heat cycle test.
  • the temperature of the electrode member 122 on the high temperature side is increased from 200 ° C. in 60 minutes, held at 600 to 700 ° C. for 30 minutes, and then controlled to decrease to 200 ° C. or less in 30 minutes. This was done until a total of 100 cycles. As a result, it was found that the power generation performance of the thermoelectric conversion module measured for each cycle was not changed and the internal resistance was not increased, and very good bonding was achieved.
  • thermoelectric conversion module After the heat cycle test, the power generation characteristics of the thermoelectric conversion module were measured under the conditions of a high temperature end of 600 ° C. and 700 ° C./low temperature end of 50 ° C. As a result, each maximum electric output was 20 to 35 W.
  • the bonding state is good, and the mutual diffusion of elements between the thermoelectric conversion member and the electrode member is I was not able to admit.
  • thermoelectric conversion modules of Examples 1 to 9 it is possible to maintain good bonding between the thermoelectric conversion members 111 to 112 and the electrode members 121 to 123 even if the temperature changes greatly due to operation or the like. was confirmed.
  • thermoelectric conversion module of this example can stably perform highly efficient power generation even when the temperature rise and fall are repeated. Thereby, it was demonstrated that the structure and manufacturing method of the thermoelectric conversion module of the present invention can alleviate thermal stress and prevent element diffusion between the thermoelectric member and the electrode member.

Abstract

Selon la présente invention, du fait qu'une contrainte thermique d'éléments d'électrode (121-123) due à une température de fonctionnement et similaire peut être relaxée au moyen de couches de relaxation de contrainte thermique (141-144), le détachement des éléments d'électrode (121-123) dû à la contrainte thermique due à la température de fonctionnement et similaire peut être éliminé de manière excellente. De plus, du fait qu'une diffusion de constituants des éléments de conversion thermoélectrique (111, 112) due à la température de fonctionnement et similaire peut être éliminée au moyen de couches de prévention de diffusion (151-154), la durabilité et la stabilité d'un module de conversion thermoélectrique (100) peuvent être améliorées.
PCT/JP2011/006512 2011-11-22 2011-11-22 Module de conversion thermoélectrique WO2013076765A1 (fr)

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US14/342,115 US9337409B2 (en) 2011-11-22 2011-11-22 Thermoelectric conversion module

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EP2784834A4 (fr) 2015-07-01

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